Eco-friendly antistatic resin composition and molded product thereof

ABSTRACT

Provided is an eco-friendly antistatic resin composition which includes: a thermoplastic resin; a conductive filler including carbon nanotubes; and one or more of coconut powder and corn powder. A molded article manufactured using the composition of the present invention has advantages in that tensile strength, impact resistance, and surface resistance are improved.

TECHNICAL FIELD

The present invention claims priority to and the benefit of the filingdate of Korean Patent Application No. 10-2021-0153985, filed with theKorean Intellectual Property Office on Nov. 10, 2021, the disclosure ofwhich is incorporated herein by reference in its entirety.

The present invention relates to an antistatic resin composition and amolded product thereof.

BACKGROUND ART

Recently, there is a demand for the development of plastic materialsusing eco-friendly materials to reduce carbon. Therefore, the use ofcarbon-reducing eco-friendly materials is also required for thedevelopment of antistatic compositions.

Electrification or static electricity is a phenomenon in which an objecttakes on electrical properties when the balance of electric charges isbroken, and is caused by physical motions and states between twoobjects, such as contact, separation, friction, and flow. An antistaticfunction refers to preventing the generation of static electricity byincreasing the electrical conductivity of an object.

Today, with the development of the electronics industry, such assemiconductors, mobile phones, displays, and secondary batteries, it isnecessary to solve malfunction issues caused by the static electricityproblem of highly integrated electronic circuits and related keycomponents, and contamination and defect problems caused by harmfulsubstances such as dust. In addition, as the need for static electricityremoval and pollution source control is particularly emphasized,research for developing an antistatic functional material havingelectrical conductivity in addition to existing properties is beingactively conducted.

An antistatic function is generally provided by applying a coating usinga conductive polymer coating agent or by adding a chemical additive suchas a hydrophilic surfactant or a conductive material such as carbonblack or a nanometal. In particular, PEDOT:PSS, which is a mainly usedconductive polymer, easily forms a coating, but the material isvulnerable to heat and ultraviolet rays, so there is a disadvantage thatthe antistatic function is significantly reduced in a short period ofone week, or six months at the most.

Conventionally, conductive fillers, surfactants, metal powders, metalfibers, and the like have been added to impart electrical conductivity.However, when a conductive filler is added to a polymer resin formanufacturing an antistatic composite material, a decrease in mechanicalproperties such as tensile strength, flexural strength, and impactstrength may occur. Therefore, it is necessary to develop a materialwith improved mechanical properties and secured electrical properties.

SUMMARY Technical Problem

The present invention is directed to providing an antistatic resincomposition having excellent mechanical properties and electricalproperties while including an eco-friendly material, and a moldedproduct thereof.

Technical Solution

One aspect of the present invention provides an eco-friendly antistaticresin composition including: a thermoplastic resin including a vinylcyanide compound-conjugated diene compound-aromatic vinyl compound graftcopolymer and one or more of polypropylene and polycarbonate; aconductive filler including carbon nanotubes; and one or moreeco-friendly fillers selected from coconut powder and corn powder.

According to one embodiment of the present invention, the thermoplasticresin may have a polydispersity index (PDI) of 5.5 to 6.5.

According to one embodiment of the present invention, the compositionmay include: 60 to 85 wt % of the thermoplastic resin; 1 to 20 wt % ofthe conductive filler; and 10 to 28 wt % of the one or more eco-friendlyfillers selected from coconut powder and corn powder, based on the totalweight thereof.

According to one embodiment of the present invention, the thermoplasticresin may include: 45 to 80 wt % of the vinyl cyanidecompound-conjugated diene compound-aromatic vinyl compound graftcopolymer; and 15 to 50 wt % of one or more of the polypropylene (PP)and the polycarbonate (PC).

According to one embodiment of the present invention, in thethermoplastic resin, a weight ratio of the polypropylene and thepolycarbonate (polypropylene:polycarbonate) may be in the range of 1:1to 1:1.5.

According to one embodiment of the present invention, the vinyl cyanidecompound-conjugated diene compound-aromatic vinyl compound graftcopolymer may have a weight-average molecular weight (Mw) of 120,000g/mol to 150,000 g/mol.

According to one embodiment of the present invention, the vinyl cyanidecompound-conjugated diene compound-aromatic vinyl compound graftcopolymer may include components (A) vinyl cyanide compound, (B)conjugated diene compound, and (C) aromatic vinyl compound having thefollowing weight-average molecular weights (Mw).

-   -   Component (A): Mw=45,000 g/mol to 55,000 g/mol    -   Component (B): Mw=50,000 g/mol to 60,000 g/mol    -   Component (C): Mw=25,000 g/mol to 35,000 g/mol

According to one embodiment of the present invention, the vinyl cyanidecompound-conjugated diene compound-aromatic vinyl compound graftcopolymer may include 9 wt % to 44 wt % of component (A), 17 wt % to 79wt % of component (B), and 9 wt % to 44 wt % of component (C), and thecontent ratio of the sum of components (A) and (C) and component (B)(i.e., sum of components (A) and (C): component (B)) may be in the rangeof 4:1 to 1:4.

According to one embodiment of the present invention, the conductivefiller may additionally include one or more of a carbon filler andcarbon black, and the content ratio of the above-described carbonnanotubes and the one or more of a carbon filler and carbon black (i.e.,carbon nanotubes: one or more of carbon filler and carbon black) may bein the range of 3:10 to 3:17 by weight.

According to one embodiment of the present invention, the surface of thecarbon nanotubes may be treated with sizing thermoplastic polyurethane.

According to one embodiment of the present invention, the melt flowindex (MI) of the thermoplastic resin may be in the range of 20 g/10 minto 50 g/10 min.

According to one embodiment of the present invention, the carbonnanotubes are single-walled carbon nanotubes, multi-walled carbonnanotubes, or a combination thereof, and the content ratio ofsingle-walled carbon nanotubes and multi-walled carbon nanotubes may bein the range of 1:99 to 50:50.

According to one embodiment of the present invention, the thermoplasticresin may additionally include one or a combination thereof selectedfrom the group consisting of polyester, polystyrene, polypropylene,polyimide, polyamide, polysulfonate, polycarbonate, polyacrylate,polyvinyl acetal, polymethylmethacrylate, polyvinyl chloride,polyethylene, modified polyphenylene oxide, SBS, SAN, synthetic rubber,a phenolic resin, an epoxy resin, an acrylic resin, and a blend orcopolymer thereof.

According to one embodiment of the present invention, the compositionmay additionally include one or more additives selected from the groupconsisting of a compatibilizer, a UV stabilizer, an antioxidant, alubricant, a heat stabilizer, a rubber, an antibacterial agent, arelease agent, a dye, an inorganic additive, a surfactant, a nucleatingagent, a coupling agent, a filler, a plasticizer, an impact modifier, anadmixture, a colorant, a stabilizer, an antistatic agent, a pigment, anda flame retardant copolymer.

According to one embodiment of the present invention, the surfaceresistance of a specimen prepared by molding the antistatic resincomposition may be in the range of 10² ohm/sq to 10⁴ ohm/sq.

According to one embodiment of the present invention, the impactstrength of a specimen prepared by molding the antistatic resincomposition may be in the range of 50 J/m to 100 J/m.

Another aspect of the present invention provides an antistatic moldedarticle manufactured and obtained by subjecting the antistatic resincomposition to an extrusion process, an injection process, or acombination thereof.

According to one embodiment of the present invention, the molded articlemay be a battery component, an electronic component transfer cart, anelectronic component packaging material, or an electronic componenttransfer tray.

Still another aspect of the present invention includes a method ofmanufacturing an antistatic molded article, which includes: preparing anantistatic resin composition; and manufacturing an antistatic moldedarticle by subjecting the antistatic resin composition to extrusion,injection, or a combination thereof.

Advantageous Effects

An antistatic resin composition of the present invention has advantagesin that since an ABS resin is blended with one or more resins selectedfrom a polycarbonate resin and a polypropylene resin, the antistaticresin composition of the present invention has excellent electricalproperties and improved mechanical properties even though it has ahigher PDI value than common thermoplastic resins including carbon black(CB) or carbon fibers (CF), which are conductive fillers.

The antistatic resin composition of the present invention has advantagesin that it has excellent electrical properties and improved mechanicalproperties while including one or more eco-friendly materials selectedfrom coconut powder and corn powder.

The antistatic resin composition of the present invention has advantagesin that although the composition includes a small amount of conductivefillers compared to general antistatic compositions including acombination of a conductive filler and a thermoplastic resin, thedesired antistatic performance of 10² ohm/sq to 10⁴ ohm/sq is attained.

The antistatic resin composition of the present invention has advantagesin that since impact strength and tensile strength, as well aselectrical properties, are maintained, the composition can be used formanufacturing molded articles such as battery components, electronicparts and modules without limitation in the form and size thereof.

DETAILED DESCRIPTION

Hereinafter, the present invention will be described in more detail.

The following description of specific functions is merely illustrativeand intended to describe embodiments according to the concept of thepresent invention, and embodiments according to the concept of thepresent invention may be implemented in various forms and should not beconstrued as being limited to the embodiments described herein.

Since the embodiments according to the concept of the present inventionmay have various modifications and various forms, only specificembodiments will be described in detail herein. However, this is notintended to limit the embodiments according to the concept of thepresent invention to the specific disclosed forms, and it should beunderstood that the embodiments according to the concept of the presentinvention include all modifications, equivalents, and substitutesincluded in the spirit and scope of the present invention.

Terms used herein are used only to describe specific embodiments and arenot intended to limit the present invention. Singular expressionsinclude plural expressions unless the context clearly dictatesotherwise.

Unless defined otherwise, all terms used herein, including technical orscientific terms, have the same meaning as commonly understood by one ofordinary skill in the art to which the present invention pertains. Termssuch as those defined in commonly used dictionaries should beinterpreted as having a meaning consistent with the meaning in thecontext of the related art and should not be interpreted in an ideal orexcessively formal sense unless explicitly defined in the presentinvention.

Hereinafter, exemplary embodiments of an antistatic resin compositionwith improved mechanical and electrical properties according to thepresent invention, a molded article thereof, and a method ofmanufacturing the same will be described in detail.

The term “composition” used herein may be used interchangeably with“composite material,” “composite,” or “mixture” in this specification,and it may be understood that the composition is formed of a combinationof two or more materials.

In addition, terms such as “molded product” and “molded article” may beused interchangeably with “processed article” herein, and the moldedproduct or molded article may be understood as a product molded into aform suitable for a purpose through the application of heat or pressure.

The present invention relates to an antistatic resin compositionincluding: a thermoplastic resin; and a conductive filler. Inparticular, aspects of the present invention provide: an antistaticresin composition with improved tensile strength and impact resistanceprepared by adjusting the content ratio of each component inside ABS sothat mechanical properties can be secured within an allowable range eventhough a conductive filler is added to a thermoplastic polymer resin;and a molded article thereof.

Thermoplastic Resin

In an antistatic resin composition according to one embodiment of thepresent invention, any type of thermoplastic resin can be used withoutparticular limitation as long as it has thermoplasticity. Specifically,as the thermoplastic resin, one or a combination thereof selected fromthe group consisting of polyester, polystyrene, polypropylene,polyimide, polyamide, polysulfonate, polycarbonate, polyacrylate,polyvinyl acetal, polymethylmethacrylate, polyvinyl chloride,polyethylene, modified polyphenylene oxide, ABS, SBS, SAN, syntheticrubber, a phenolic resin, an epoxy resin, an acrylic resin, and a blendor copolymer thereof, can be used.

More specifically, the thermoplastic resin may include a vinyl cyanidecompound-conjugated diene compound-aromatic vinyl compound graftcopolymer and any one or more of polypropylene (PP) and polycarbonate(PC).

The thermoplastic resin has a weight-average molecular weight tonumber-average molecular weight ratio (PDI) of 5.5 to 6.5.

A polydispersity index (PDI), which is defined as a ratio ofweight-average molecular weight (Mw) to number-average molecular weight(Mn), is a standard indicating the width of a molecular weightdistribution of a polymer.

In general, when synthesizing a polymer compound, a polymer chain isformed, and the polymer has different molecular weights according to adegree of polymerization. A measure for indicating the width of themolecular weight distribution is a polydispersity index (PDI). Thehigher the PDI, the wider the molecular weight distribution, which meansthat the polymer has chains with very high molecular weight, chains withvery low molecular weight, or both. That is, a polymer with a high PDIvalue is formed of molecular chains of various lengths. In general,chains with very high molecular weight or chains with very low molecularweight may affect the mechanical properties of the polymer. The closerthe PDI is to 1, the closer the polymer is to a single molecular-weightpolymer with good physical properties.

The thermoplastic resin of the present invention includes polypropylene(PP) and polycarbonate (PC) in addition to a vinyl cyanidecompound-conjugated diene compound-aromatic vinyl compound graftcopolymer, so it has excellent properties while having a high PDI value.

Specifically, the thermoplastic resin may include 45 to 80 wt % of thevinyl cyanide compound-conjugated diene compound-aromatic vinyl compoundgraft copolymer and any one of 15 to 50 wt % of polypropylene (PP), 15to 50 wt % of polycarbonate (PC), or 15 to 50% of a combination ofpolypropylene (PP) and polycarbonate (PC). More specifically, thethermoplastic resin may include 47 to 77 wt % of the vinyl cyanidecompound-conjugated diene compound-aromatic vinyl compound graftcopolymer and 25 to 45 wt % of any one of polypropylene (PP),polycarbonate (PC), or a combination of polypropylene (PP) andpolycarbonate (PC).

Carbon nanotubes (CNTs) used as a conductive filler in the presentinvention tend to be distributed in a region having a low melt viscosityunder the condition of a composite resin including two or more resins.When the content of polypropylene (PP), polycarbonate (PC), or acombination of polypropylene (PP) and polycarbonate (PC) is lower thanthe content of the ABS resin, the CNTs are distributed on the surface ofpolypropylene, polycarbonate, or a combination of polypropylene andpolycarbonate, so surface resistance is lowered, and the excellentphysical properties of ABS can be utilized.

On the other hand, when the content of the ABS resin is higher than thecontent of polypropylene, polycarbonate, or a combination ofpolypropylene and polycarbonate, carbon nanotubes (CNTs) are distributedin the ABS resin, so the physical properties such as impact strength andtensile strength and electrical properties such as surface resistance ofthe ABS resin itself are lowered.

According to one embodiment of the present invention, the thermoplasticresin may include 45 to 80 wt % of the vinyl cyanide compound-conjugateddiene compound-aromatic vinyl compound graft copolymer and 15 to 50 wt %of one or more of the polypropylene (PP) and the polycarbonate (PC), andin this case, there is an effect that electrical properties includingsurface resistance and mechanical properties including impact resistanceand tensile strength are excellent despite a high PDI value.

According to one embodiment of the present invention, the thermoplasticresin may include 45 to 80 wt % of the vinyl cyanide compound-conjugateddiene compound-aromatic vinyl compound graft copolymer and 15 to 50 wt %of a combination of the polypropylene and the polycarbonate.

When a combination of the polypropylene and the polycarbonate isincluded, there is an effect that electrical properties includingsurface resistance and mechanical properties including impact resistanceand tensile strength are excellent despite a high PDI value.

Specifically, the thermoplastic resin may include 47 to 77 wt % of theacrylonitrile-butadiene-styrene copolymer and, in addition, any one of25 to 45 wt % of polypropylene (PP), 25 to 45 wt % of polycarbonate(PC), or 20 to 25% of a combination of polypropylene (PP) andpolycarbonate (PC).

When the combination of polypropylene and polycarbonate is used, thecombination may include 8 to 25 wt % of polypropylene and 11 to 27 wt %of polycarbonate.

When the combination of polypropylene and polycarbonate is used, theweight ratio of the polypropylene and the polycarbonate(polypropylene:polycarbonate) may be in the range of 1:1 to 1:1.5.

When the combination of polypropylene and polycarbonate is included inaddition to the acrylonitrile-butadiene-styrene copolymer, apolydispersity index (PDI) may be in the range of 5.5 to 6.5. In thiscase, other polymer resins may be additionally included or blended.

In the vinyl cyanide compound-conjugated diene compound-aromatic vinylcompound graft copolymer, the vinyl cyanide compound may be, forexample, acrylonitrile, methacrylonitrile, or a combination thereof. Theconjugated diene compound may be, for example, one or more selected fromthe group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene,2-ethyl-1,3-butadiene, 1,3-pentadiene, isoprene, chloroprene, andpiperylene. The aromatic vinyl compound may be, for example, one or moreselected from the group consisting of styrene, α-methyl styrene,vinyltoluene, and chlorostyrene.

Among components forming the vinyl cyanide compound-conjugated dienecompound-aromatic vinyl compound graft copolymer, the vinyl cyanidecompound, particularly acrylonitrile, is a component that may have aneffect of improving mechanical properties such as hardness, tensilestrength, elastic modulus, and impact resistance, the conjugated dienecompound, particularly, butadiene, is a component that may have aneffect of improving impact resistance, abrasion resistance, and thelike, and the aromatic vinyl compound, particularly, styrene, is acomponent that may affect moldability, electrical properties, and thelike.

In particular, among the vinyl cyanide compound-conjugated dienecompound-aromatic vinyl compound graft copolymers, an ABS resin is abutadiene resin grafted with styrene and acrylonitrile, and by adjustingthe proportion of styrene and acrylonitrile (SAN=styrene+acrylonitrile)and the proportion of butadiene, it is possible to improve mechanicalproperties such as the impact strength, elastic modulus, and tensilestrength of the ABS resin and electrical properties such as surfaceresistance.

The vinyl cyanide compound-conjugated diene compound-aromatic vinylcompound graft copolymer may have a weight-average molecular weight (Mw)of 70,000 g/mol to 250,000 g/mol, specifically, 100,000 g/mol to 200,000g/mol, and more specifically, 120,000 g/mol to 150,000 g/mol, and whenthis range is satisfied, mechanical properties are excellent.

The vinyl cyanide compound-conjugated diene compound-aromatic vinylcompound graft copolymer may include components (A) vinyl cyanidecompound, (B) conjugated diene compound, and (C) aromatic vinylcompound, and the weight-average molecular weights (Mw) of thecomponents are as follows.

-   -   Component (A): Mw=45,000 g/mol to 55,000 g/mol,    -   Component (B): Mw=50,000 g/mol to 60,000 g/mol,    -   Component (C): Mw=25,000 g/mol to 35,000 g/mol.

According to one embodiment of the present invention, concerning thecontent ratio of components forming the vinyl cyanidecompound-conjugated diene compound-aromatic vinyl compound graftcopolymer, as the proportion of the vinyl cyanide compound and thearomatic vinyl compound increases, tensile strength is improved, and asthe proportion of the conjugated diene compound increases, impactstrength is improved. In addition, there is a tendency that as theproportion of the conjugated diene compound increases, a melt flow index(MI) value decreases.

As one example of the vinyl cyanide compound-conjugated dienecompound-aromatic vinyl compound graft copolymer, in the case of an ABSresin, mechanical properties and processability can be improved byadjusting, among various factors affecting impact strength, theproportion of SAN (acrylonitrile+styrene) and the proportion ofbutadiene in consideration of factors due to an adhesive effect betweenSAN (acrylonitrile+styrene) regions and Butadiene.

The vinyl cyanide compound-conjugated diene compound-aromatic vinylcompound graft copolymer may include 9 wt % to 44 wt % of component (A),17 wt % to 79 wt % of component (B), and 9 wt % to 44 wt % of component(C). The content ratio of the sum of components (A) and (C) andcomponent (B) (i.e., sum of components (A) and (C): component (B)) maybe in the range of 4:1 to 1:4.

Specifically, the vinyl cyanide compound-conjugated dienecompound-aromatic vinyl compound graft copolymer may include 15 wt % to34 wt % of component (A), 33 wt % to 69 wt % of component (B), and 15 wt% to 34 wt % of component (C), and the content ratio of the sum ofcomponents (A) and (C) and component (B) may be in the range of 2:1 to1:2.

Here, the wt % is obtained based on 100 wt % of the total weight of theconjugated diene rubber, the vinyl cyanide compound, and the aromaticvinyl compound.

According to one embodiment of the present invention, the thermoplasticresin may include the vinyl cyanide compound-conjugated dienecompound-aromatic vinyl compound graft copolymer and another polymerresin or may be a blend thereof.

As the other polymer resin, any type of polymer resin can be usedwithout particular limitation as long as it has thermoplasticity.Specifically, as the thermoplastic resin, one or a combination thereofselected from the group consisting of polyester, polystyrene,polypropylene, polyimide, polyimide, polysulfonate, polycarbonate,polyacrylate, polyvinyl acetal, polymethylmethacrylate, polyvinylchloride, polyethylene, modified polyphenylene oxide, SBS, SAN,synthetic rubber, a phenolic resin, an epoxy resin, an acrylic resin,and a blend or copolymer thereof, can be used.

The melt flow index (MI) of the thermoplastic resin of the presentinvention may be in the range of specifically 20 to 50 g/10 min and morespecifically 22 to 45 g/10 min.

A melt flow index (MI) is a flow rate when a thermoplastic polymer meltis extruded from a piston under specific conditions and indicates howeasily the melt flows. That is, the melt flow index can be used forunderstanding the flowability of polymer materials. In general, thehigher the molecular weight, the lower the MI. When the MI is high,injection moldability is excellent, and when the MI is low, it isadvantageous for extrusion. When the MI of the thermoplastic resin ofthe present invention is in the range of 20 g/10 min to 50 g/10 min,there is an advantage that the resin can be appropriately used for bothinjection molding and extrusion.

Eco-Friendly Filler

The eco-friendly filler may be one or more of coconut powder and cornpowder and may be used in an amount of 10 wt % or more, 15 wt % or more,20 wt % or more, and 30 wt % or less, 28 wt % or less, 26 wt % or lessbased on the total weight of the composition. When the eco-friendlyfiller is used in an amount of more than 30 wt %, mechanical propertiessuch as impact strength, tensile strength, and a MI value may belowered.

Conductive Filler

A conductive filler according to one embodiment of the present inventionmay include carbon nanotubes. The conductive filler may include carbonnanotubes (CNTs), and the conductive filler may be included in an amountof 1 wt % to 40 wt % based on the total weight of the composition.

The carbon nanotube can improve the impact strength and tensile strengthof the thermoplastic resin and, at the same time, improve theconductivity of a thermally conductive resin. In general, carbonnanotubes are tubular materials formed of carbons connected in ahexagonal ring shape and have a diameter of several to several tens ofnanometers. Carbon nanotubes are not damaged or abraded even whencontinuously or repeatedly used, are chemically stable, and haveexcellent thermal and electrical properties, so they have variousapplications, such as electromagnetic absorbers, antistatic agents,field emission devices, semiconductor devices, gas sensors andbiosensors, fuel cells, and reinforcement agents.

The carbon nanotube according to one embodiment of the present inventionis a material for imparting electrical conductivity to the thermoplasticpolymer resin having low electrical conductivity, and in a productmanufactured by molding a resin composition to which it is added, thecarbon nanotube can improve electrical conductivity by reducing thesurface resistance of the product and thus can improve antistaticproperties. Specifically, when carbon nanotube aggregates are mixed withthe thermoplastic polymer resin, a continuous three-dimensional networkcan be formed as individual carbon nanotubes are dispersed in thethermoplastic polymer resin and connected to one another, andaccordingly, excellent electrical conductivity can be exhibited.

The carbon nanotube of the present invention may include single-walledcarbon nanotubes, multi-walled carbon nanotubes, or a combinationthereof. Specifically, carbon nanotubes in which the content ratio ofthe single-walled carbon nanotubes and the multi-walled carbon nanotubesis in the range of 0.1:99.9 to 50:50 may be used, and more specifically,multi-walled carbon nanotubes are preferably used. More specifically, itis preferable to use carbon nanotubes having an average diameter of 5 nmto 20 nm and an aspect ratio of 100 to 10,000 so that degradation ofphysical properties can be minimized and antistatic properties can beexhibited in the case of kneading with the thermoplastic resin. It iscommercially advantageous to use multi-walled carbon nanotubes which arerelatively inexpensive and have high purity compared to single-walledcarbon nanotubes, which are expensive and have a relatively highimpurity content. In addition, compared to single-walled carbonnanotubes, multi-walled carbon nanotubes are less likely to be damaged(e.g., broken) in a composite forming process and retain a longer lengthafter the process, and thus can make a greater contribution to improvingthe mechanical strength and electrical conductivity of a compositematerial obtained as a result of the process.

Methods for synthesizing the carbon nanotubes include an arc-dischargemethod, a pyrolysis method, a laser vaporization method, a plasmachemical vapor deposition method, a thermal chemical vapor depositionmethod, and the like, but all synthesized carbon nanotubes can be usedwithout limitation to a synthesis method thereof.

According to one embodiment of the present invention, the carbonnanotubes are preferably used in an amount of 1 wt % to 40 wt %,specifically, 1 wt % to 20 wt %, more specifically, 3 wt % to 20 wt %,and when the usage amount is less than 1 wt %, antistatic performance isnot well exhibited, and when the usage amount is more than 20 wt %,flowability is lowered, the occurrence of surface defects increases, anddesired mechanical properties are not easily obtained.

As the multi-walled carbon nanotubes, bundle-type carbon nanotubes ornon-bundle-type carbon nanotubes can be used without limitation.

As used herein, the term “bundle” refers to a bundle or rope form inwhich a plurality of carbon nanotubes are arranged in parallel orentangled unless otherwise specified. The term “non-bundle orentangled-type” refers to a form that does not have a specific form suchas the above-described bundle or rope form.

The bundle-type multi-walled carbon nanotubes may have a form in which aplurality of multi-walled carbon nanotube strands are basically gatheredto form a bundle, and the plurality of strands have a linear form, acurved form, or a combination thereof. In addition, the bundle-typecarbon nanotubes may also have a linear form, a curved form, or acombination thereof.

According to one embodiment of the present invention, the conductivefiller may additionally include a carbon filler and/or carbon black. Thecontent ratio of carbon nanotubes:carbon filler and/or carbon black maybe in the range of 3:10 to 3:17.

According to one embodiment of the present invention, the surface of thecarbon nanotubes may be treated with sizing a polymer resin sizingagent. Specifically, the sizing agent may be one or more selected fromthe group consisting of an epoxy-based resin, a phenoxy-based resin,polyurethane, thermoplastic polyurethane (TPU) polyetherimide,polyamide, polypropylene, nitric acid, and maleic anhydride, and morespecifically, TPU.

A resin polymer is covalently bonded with a sizing agent, so a stronginterfacial bonding force is formed, and since the sizing agent modifiesthe surface properties of carbon fiber, a polymer polymerized by aseparate initiator can also form a better interfacial bond with carbonfiber than before, and the polymerized polymer has the same chemicalstructure as the sizing agent and thus is easily bonded to the same.

In this case, the method of applying the sizing agent is notparticularly limited, and for example, the sizing agent may be appliedby a dipping method, a roll coating method, a die coating method, agravure coating method, a spray coating method, a flow coating method,or the like, but the present invention is not limited thereto.

Antistatic Resin Composition

An antistatic resin composition according to one embodiment of thepresent invention may additionally include other additives. Theantistatic resin composition may additionally include 0.01 wt % to 10 wt% of a compatibilizer, 0.01 wt % to 10 wt % of an additive, and 0.01 wt% to 60 wt % of rubber, and the other additives may be one or moreselected from the group consisting of a compatibilizer, a UV stabilizer,an antioxidant, a lubricant, a heat stabilizer, a rubber, anantibacterial agent, a release agent, a dye, an inorganic additive, asurfactant, a nucleating agent, a coupling agent, a filler, aplasticizer, an impact modifier, an admixture, a colorant, a stabilizer,an antistatic agent, a pigment, and a flame retardant copolymer.

The surface resistance of a specimen prepared by molding the antistaticresin composition according to one embodiment of the present inventionmay be in the range of 10² ohm/sq to 10¹⁰ ohm/sq, specifically, 10²ohm/sq to 10⁴ ohm/sq.

The impact strength of a specimen prepared by molding the antistaticresin composition according to one embodiment of the present inventionmay be in the range of 30 J/m to 500 J/m, specifically, 50 J/m to 100J/m.

The tensile strength of a specimen prepared by molding the antistaticresin composition according to one embodiment of the present inventionmay be in the range of 45 MPa to 100 MPa, specifically, 75 MPa to 95MPa.

The antistatic resin composition of the present invention can be formedinto a molded article through extrusion, injection, or a combinationthereof and applied to an antistatic product requiring strength andelectrical conductivity, but a method of manufacturing the moldedarticle is not limited to those disclosed above, and a method commonlyused in the art can be appropriately used.

Specifically, one aspect of the present invention provides a method ofmanufacturing an antistatic molded product, which includes: preparing anantistatic resin composition by mixing the thermoplastic resin includinga vinyl cyanide compound (A)-conjugated diene compound (B)-aromaticvinyl compound (C) graft copolymer, the conductive filler includingcarbon nanotubes, and the one or more eco-friendly fillers selected fromcorn powder and coconut powder; and forming an antistatic molded productby subjecting the composition to an extrusion process, an injectionprocess, or a combination thereof.

The conductive filler may be included in an amount of 3 to 20 wt % ofthe total weight of the composition, and component (A), component (B),and component (C) may be included in an amount of 15 to 34 wt %, 33 wt %to 69 wt %, and 15 to 34 wt %, respectively, and the weight ratio of thesum of components (A) and (C) and component (B) may be in the range of2:1 to 1:2.

Specific examples of the molded article that can be formed by the abovemethod include a battery component, an electronic component transfercart, an electronic component transfer pipe-coating material, anelectronic component for thermoforming, and the like, but the presentinvention is not limited thereto.

Hereinafter, embodiments of the present invention will be described indetail so that those of ordinary skill in the art to which the presentinvention pertains can easily carry out the present invention. However,the present invention may be implemented in several different forms andis not limited to the embodiments described herein.

Example 1

43 wt % of an ABS resin, 37 wt % of polypropylene (PP), 10 wt % ofcoconut powder, 10 wt % of corn powder, and 3% of carbon nanotubes(multi-walled carbon nanotubes) were uniformly mixed so that the totalamount was 100 wt %.

The weight ratio of SAN and Butadiene in the ABS resin was maintained at1:1 (Acrylonitrile:Butadiene:Styrene=7:14:7). To measure variousproperties, based on the mixed antistatic resin composition, impact testspecimens (thickness: 6 mm), tensile strength test specimens (thickness:3 mm), and surface resistance test specimens (thickness: 3 mm) wereprepared using an extruder and an injection machine.

Example 2

A composition was prepared in the same manner as in Example 1 exceptthat a component weight ratio different from a weight ratio in Example 1was used.

Example 3

40 wt % of an ABS resin, 15 wt % of polypropylene (PP), 20 wt % ofpolycarbonate (PC), 12 wt % of coconut powder, 13 wt % of corn powder,and 3% of carbon nanotubes (multi-walled carbon nanotubes) wereuniformly mixed so that the total amount was 100 wt %, and thecomposition was prepared in the same manner as in Example 1.

Comparative Examples 1 to 3

Comparative Examples 1 and 2 were prepared in the same manner as inExample 1 except that a component weight ratio different from a weightratio in Example 1 was used, and Comparative Example 3 was prepared inthe same manner as in Example 3 except that a weight ratio differentfrom a weight ratio in Example 3 was used.

Comparative Examples 4 to 28

Comparative Examples 4 to 28 were prepared while varying the weight ofeach component without using the coconut powder and corn powder ofExamples 1 to 3.

Experimental Example 1: Measurement of Surface Resistance

The surface resistance of specimens prepared according to theabove-described Examples and Comparative Examples was measured asfollows.

The surface resistance was measured by a four-probe method using aKeithley 6220 current source and a 2182A nanovoltmeter in accordancewith ASTM standard D257 under a condition of a composite materialthickness of 3 mm.

The results of measuring the surface resistance are shown in Table 1.

Experimental Example 2: Measurement of Impact Strength

The impact strength of specimens prepared according to theabove-described Examples and Comparative Examples was measured asfollows.

After forming a notch on impact test specimens (thickness: 6 mm) using anotching machine, impact strength (J/m) was measured using an Izodimpact tester in accordance with ASTM standard D-256.

The results of measuring the impact strength are shown in Table 1.

Experimental Example 3: Measurement of Tensile Strength

The tensile strength of specimens prepared according to theabove-described Examples and Comparative Examples was measured asfollows.

The tensile strength (MPa) of tensile strength test specimens(thickness: 3 mm) was measured in accordance with ASTM standard D638using a universal testing machine (UTM).

The results of measuring the tensile strength are shown in Table 1.

Experimental Example 4: Measurement of MI

The MI of compositions prepared in the above-described Examples andComparative Examples was measured in accordance with ASTM standard D1238using a melt flow index (g/10 min) tester.

The results of measuring the MI are shown in Table 1.

Experimental Example 5: Measurement of PDI

The polydispersity index (PDI) of ABS in the compositions prepared inthe above-described Examples and Comparative Examples was measured bygel permeation chromatography (GPC).

The results of measuring the PDI are shown in Table 1.

TABLE 1 Eco-friendly Properties Thermoplastic ABS mixing fillerConductive Surface Impact Tensile resin ratio Coconut Corn fillerresistance strength strength MI (g/ Classification ABS PP PC Total A B Spowder powder CNT (ohm/sq) (J/m) (MPa) 10 min) PDI Example 1 43 37 80 12 1 10 10 3 104 55 75 40 6.44 Example 2 40 35 75 1 2 1 12 13 3 104 50 7044 6.21 Example 3 40 15 20 75 1 2 1 12 13 3 102 85 75 40 6.5 Comparative38 32 70 15 15 3 104 40 50 48 6.9 Example 1 Comparative 32 28 60 20 20 3104 40 61 60 7.8 Example 2 Comparative 38 14 18 15 15 3 102 70 60 58 7.6Example 3 Comparative 52 45 — 97 1 2 1 3 104 89 78 25 5.59 Example 4Comparative 47 40 — 87 1 2 1 13 104 90 75 22 6.24 Example 5 Comparative67 30 — 97 1 2 1 3 103 93 86 32 5.59 Example 6 Comparative 57 25 — 82 12 1 18 103 99 88 40 5.84 Example 7 Comparative 77 20 — 97 1 2 1 3 104110 97 27 6.24 Example 8 Comparative 60 20 — 80 1 2 1 20 104 120 95 325.84 Example 9 Comparative 52 20 25 97 1 2 1 3 102 140 85 26 5.84Example 10 Comparative 67 13 17 97 1 2 1 3 102 170 95 46 6.1 Example 11Comparative 77  9 11 97 1 2 1 3 103 200 99 40 5.59 Example 12Comparative 67 30 97 1 8 1 3 103 120 99 25 5.59 Example 13 Comparative67 30 97 1 2 1 3 104 116 95 22 6.24 Example 14 Comparative 67 30 97 2 12 3 103 100 97 32 5.59 Example 15 Comparative 67 13 17 97 1 8 1 3 103180 94 40 5.84 Example 16 Comparative 67 13 17 97 1 2 1 3 103 190 96 255.59 Example 17 Comparative 67 13 17 97 2 1 2 3 103 200 95 22 6.24Example 18 Comparative 40 57 — 97 3 5 2 3 109 29 52 75 5.58 Example 19Comparative 35 62 — 97 3 5 2 3 108 25 41 57 5.84 Example 20 Comparative30 — 67 97 3 5 2 3 107 21 66 60 6.2 Example 21 Comparative 97 — — 97 316 3 3 108 80 20 101 5.54 Example 22 Comparative 25 36 36 97 1 2 1 3 10925 30 0.4 6 Example 23 Comparative 11 43 43 97 1 2 1 3 109 20 35 0.2 7Example 24 Comparative 67 30 97 1 10 1 3 107 55 25 20 6.24 Example 25Comparative 67 30 97 5 2 5 3 108 30 40 16 5.59 Example 26 Comparative 6713 17 97 1 10 1 3 107 75 22 10 5.84 Example 27 Comparative 67 13 17 97 52 5 3 108 44 30 9 5.59 Example 28

In the case of Examples 1 to 3, it can be seen that when an eco-friendlyfiller was used in an amount of 20% or more in accordance with the EL727standard, there was no significant effect on electrical properties, andin the case of Comparative Examples 1 to 3, it can be seen that when aneco-friendly filler was used in an amount of 30% or more, mechanicalproperties were significantly lowered.

In the case of the resin compositions obtained according to theabove-described Comparative Examples 4 to 12, it can be seen thatelectrical properties and mechanical properties including impactstrength and tensile strength were excellent. In particular, in the caseof Comparative Examples 10 to 12, it can be seen that sincepolypropylene (PP) and polycarbonate (PC) were mixed with an ABS resin,electrical properties, impact strength, and tensile strength were moreimproved than when only polypropylene (PP) was mixed with an ABS resin.In the case of Comparative Examples 19 to 28, it can be seen thatelectrical properties and mechanical properties were significantlylowered.

In the case of Examples 1 to 3, it can be seen that electricalproperties and mechanical properties were excellent, similarly toComparative Examples 4 to 18 which did not include an eco-friendlyfiller.

As described above, exemplary embodiments have been disclosed in thedrawings and the specification. Although specific terms have been usedherein, the terms are used only to describe the present invention andare not used to limit meanings or the scope of the present inventiondefined in the claims. Therefore, it will be understood by those ofordinary skill in the art that various modifications and equivalentexamples are possible therefrom. Therefore, the true technicalprotection scope of the present invention should be defined by thetechnical spirit of the appended claims.

1. An eco-friendly antistatic resin composition comprising: athermoplastic resin including a vinyl cyanide compound-conjugated dienecompound-aromatic vinyl compound graft copolymer and any one or more ofpolypropylene and polycarbonate; a conductive filler including carbonnanotubes; and one or more of coconut powder and corn powder.
 2. Theeco-friendly antistatic resin composition of claim 1, wherein thethermoplastic resin has a polydispersity index (PDI) of 5.5 to 6.5. 3.The eco-friendly antistatic resin composition of claim 1, wherein thecomposition includes: 60 wt % to 85 wt % of the thermoplastic resin; 1wt % to 20 wt % of the conductive filler; and 10 wt % to 28 wt % of theone or more of coconut powder and corn powder, based on the total weightthereof.
 4. The eco-friendly antistatic resin composition of claim 3,wherein the thermoplastic resin includes: 45 wt % to 80 wt % of thevinyl cyanide compound-conjugated diene compound-aromatic vinyl compoundgraft copolymer; and 15 wt % to 50 wt % of the polypropylene and thepolycarbonate, wherein a weight ratio of the polypropylene and thepolycarbonate is in the range of 1:1 to 1:1.5.
 5. The antistatic resincomposition of claim 1, wherein the vinyl cyanide compound-conjugateddiene compound-aromatic vinyl compound graft copolymer includescomponents (A) vinyl cyanide compound, (B) conjugated diene compound,(C) aromatic vinyl compound having the following weight-averagemolecular weights (Mw): component (A): Mw=45,000 g/mol to 55,000 g/mol,component (B): Mw=50,000 g/mol to 60,000 g/mol, component (C): Mw=25,000g/mol to 35,000 g/mol.
 6. The antistatic resin composition of claim 1,wherein the vinyl cyanide compound-conjugated diene compound-aromaticvinyl compound graft copolymer includes: 9 wt % to 44 wt % of thecomponent (A); 17 wt % to 79 wt % of the component (B); and 9 wt % to 44wt % of the component (C), wherein a content ratio of the sum of thecomponents (A) and (C) and the component (B) is in the range of 4:1 to1:4.
 7. The antistatic resin composition of claim 1, wherein theconductive filler includes one or more of a carbon filler and carbonblack, and a content ratio of the carbon nanotubes and the one or moreof a carbon filler and carbon black is in the range of 3:10 to 3:17 byweight.
 8. The antistatic resin composition of claim 1, wherein asurface of the carbon nanotubes is treated with sizing thermoplasticpolyurethane.
 9. The antistatic resin composition of claim 1, whereinthe thermoplastic resin has a melt flow index (MI) of 20 g/10 min to 50g/10 min.
 10. The antistatic resin composition of claim 1, wherein thethermoplastic resin further includes one or more selected from the groupconsisting of polyester, polystyrene, polypropylene, polyimide,polyamide, polysulfonate, polycarbonate, polyacrylate, polyvinyl acetal,polymethylmethacrylate, polyvinyl chloride, polyethylene, modifiedpolyphenylene oxide, SBS, SAN, synthetic rubber, a phenolic resin, anepoxy resin, an acrylic resin, a blend thereof, and a copolymer thereof.11. The antistatic resin composition of claim 1, wherein the compositionadditionally includes one or more additives selected from the groupconsisting of a compatibilizer, a UV stabilizer, an antioxidant, alubricant, a heat stabilizer, a rubber, an antibacterial agent, arelease agent, a dye, an inorganic additive, a surfactant, a nucleatingagent, a coupling agent, a filler, a plasticizer, an impact modifier, anadmixture, a colorant, a stabilizer, an antistatic agent, a pigment, anda flame retardant.
 12. The antistatic resin composition of claim 1,wherein the surface resistance of a specimen prepared by molding theantistatic resin composition is in the range of 10² ohm/sq to 10⁴ohm/sq.
 13. The antistatic resin composition of claim 1, wherein theimpact strength of a specimen prepared by molding the antistatic resincomposition is in the range of 50 J/m to 100 J/m.
 14. An antistaticmolded article manufactured and obtained by subjecting the antistaticresin composition of claim 1 to an extrusion process, an injectionprocess, or a combination thereof.
 15. The antistatic molded article ofclaim 14, wherein the molded article is a battery component, anelectronic component transfer cart, an electronic component packagingmaterial, or an electronic component transfer tray.